EP4339240A1 - Compositions de polyoléfines obtenues à partir de polyoléfines recyclées - Google Patents

Compositions de polyoléfines obtenues à partir de polyoléfines recyclées Download PDF

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Publication number
EP4339240A1
EP4339240A1 EP22195654.3A EP22195654A EP4339240A1 EP 4339240 A1 EP4339240 A1 EP 4339240A1 EP 22195654 A EP22195654 A EP 22195654A EP 4339240 A1 EP4339240 A1 EP 4339240A1
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EP
European Patent Office
Prior art keywords
ranging
iso
components
anyone
measured
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP22195654.3A
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German (de)
English (en)
Inventor
Stefano Spataro
Davide TARTARI
Cristina COVA
Claudio Cavalieri
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Basell Poliolefine Italia SRL
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Basell Poliolefine Italia SRL
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Priority to EP22195654.3A priority Critical patent/EP4339240A1/fr
Publication of EP4339240A1 publication Critical patent/EP4339240A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

Definitions

  • the present disclosure relates to polyolefin compositions containing recycled polyethylene that can be used in injection molded articles particularly for grates and pails.
  • Polyolefin compositions for this use are described in WO2006/125720 as being made of a) 65-77%, preferably 70 to 77%, of a crystalline propylene polymer having an amount of isotactic pentads (mmmm), measured by 13C-MNR on the fraction insoluble in xylene at 25°C, higher than 97.5 molar % and a polydispersity index ranging from 5 to 10; b) 8 to less than 13%, preferably 9 to 12%, of an elastomeric copolymer of ethylene and propylene, the copolymer having an amount of recurring units deriving from ethylene ranging from 30 to 70%, preferably 35 to 60%, and being partially soluble in xylene at ambient temperature; the polymer fraction soluble in xylene at ambient temperature having an intrinsic viscosity value ranging from 2 to 4 dl/g; and c) 10-23%, preferably 10 to 20%, of polyethylene having an intrinsic viscosity value ranging from
  • Polyolefin compositions suitable for these applications are endowed with good stiffness, impact resistance and stress-whitening resistance.
  • polyolefin compositions although being appreciated in terms of performances, give raise to concerns in terms of sustainability with particular reference to the fact that their production is based on the use of non-renewable sources.
  • variable amounts of recycled polyolefins such as polypropylene or polyethylene.
  • the recycled polyolefin derive from streams of post-consumer waste (PCW) material that undergoes various step of separation from other polymers, such as PVC, PET or PS.
  • PCW post-consumer waste
  • PCW post-consumer waste
  • PP polypropylene
  • PE polyethylene
  • PCW post-consumer waste
  • rPE recycled PE
  • rPP recycled PP
  • polypropylene composition comprising:
  • polypropylene composition comprising:
  • copolymer refers to both polymers with two different recurring units and polymers with more than two different recurring units, such as terpolymers, in the chain.
  • ambient temperature is meant therein a temperature of 25 °C (room temperature).
  • crystalline propylene polymer in the present application a propylene polymer having an amount of isotactic pentads (mmmm), measured by 13C-MNR on the fraction insoluble in xylene at 25° C, higher than 70 molar %; by "elastomeric” polymer is meant a polymer having solubility in xylene at ambient temperature higher than 50 wt%.
  • Crystalline propylene polymer (a) is selected from a propylene homopolymer and a copolymer of propylene containing at most 3.0 wt% of ethylene or a C4-C10 ⁇ -olefin or combination thereof. Particularly preferred is the propylene homopolymer.
  • the polydispersity Index ranges from 3 to 10.
  • the r-PE ( c) is crystalline or semicrystalline high density PE (r-HDPE) selected from commercial PCW (Post Consumer Waste for example from municipality).
  • r-PE (c) has a density (ISO 1183-1) ranging from 0.940 g/cm3 to 0.965 g/cm3 and a melt flow rate (ISO 1133-1 190°C/2.16 Kg) from 0.1 to 1.0 g/10 min.
  • the plastic mixture containing rHDPE Prior its use, the plastic mixture containing rHDPE undergoes standard recycling process including collection, shredding, sorting and washing.
  • the sorted rHDPE is constituted by a large preponderance of HDPE it invariably contains minor amounts of other polymeric and/or inorganic components.
  • the r-PE according to the present disclosure contains inclusion of polypropylene in an amount from 1 wt% to 15 wt% preferably from 5wt% up to 10wt% of the total r-PE component.
  • the r-PE includes a crystalline polyethylene fraction in which in which the amount of recurring units derived from propylene in the polyethylene chains is lower than 11 wt% and most preferably they are absent, i.e, most preferably r-PE is ethylene homopolymer containing the above mentioned inclusions.
  • the (r-PE) has a melt flow rate (190°C/2.16 Kg ISO 1133-1) from 0.1 to 1.0 g/lOmin and more preferably from 0.1 to 0.5 g/lOmin.
  • the r-PE is commercially available.
  • An example of a suitable r-PE grade is represented by the grade sold by Lyondellbasell under the tradename Hostalen QCP5603 in the ivory or grey versions.
  • composition of the present disclosure preferably shows a tensile modulus value of at least 1000 MPa, preferably from 1100 to 1700 MPa, even more preferably from 1150 MPa, to 1600 MPa.
  • the value of Charpy impact resistance at 23° C is preferably higher than 4.0 kJ/m2, preferably ranges from 4.5 to 15.0 kJ/m2, more preferably ranges from 5.0 to 10.0 kJ/m2; the Charpy impact resistance at 0° C is preferably more than 3.0 kJ/m2, preferably ranges from 3.0 to 8.0 kJ/m2, more preferably ranges from 3.5 to 7.0 kJ/m2 and the Charpy impact resistance at -20° C is preferably of at least 1.5 kJ/m2 ;preferably ranges from 2.0 to 7.0 kJ/m2 .
  • composition of the present disclosure can be obtained by mechanical blending of the components (a)-(c) according to conventional techniques.
  • component (c) is mechanically blended with a preformed heterophasic composition comprising components (a) and (b) associated together by means of a sequential copolymerization process.
  • the said process comprises polymerizing propylene alone or in mixture with a low amount of ethylene in a first stage and then, in a second stage, polymerizing propylene with a higher amount of ethylene, both stages being conducted in the presence of a catalyst comprising the product of the reaction between:
  • the internal donor is preferably selected from the esters of mono or dicarboxylic organic acids such as benzoates, malonates, phthalates and certain succinates. Examples of internal donors are described in US 4522930A , EP 045977A2 and international patent applications WO 00/63261 and WO 01/57099 . Particularly suited are the phthalic acid esters and succinate acids esters. Alkylphthalates are preferred, such as diisobutyl, dioctyl and diphenyl phthalate and benzyl-butyl phthalate.
  • the particles of solid component (i) may have substantially spherical morphology and average diameter ranging between 5 and 150 ⁇ m, preferably from 20 to 100 ⁇ m and more preferably from 30 to 90 ⁇ m.
  • particles having substantially spherical morphology those are meant wherein the ratio between the greater axis and the smaller axis is equal to or lower than 1.5 and preferably lower than 1.3.
  • the amount of Mg may preferably range from 8 to 30% more preferably from 10 to 25wt. %.
  • the amount of Ti may range from 0.5 to 7% and more preferably from 0.7 to 5wt. %.
  • the solid catalyst component (i) can be prepared by reacting a titanium compound of formula Ti(OR)q-yXy, where q is the valence of titanium and y is a number between 1 and q, preferably TiCl4, with a magnesium chloride deriving from an adduct of formula MgCl2•pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
  • the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride, operating under stirring conditions at the melting temperature of the adduct (100-130°C).
  • the adduct is mixed with an inert hydrocarbon immiscible with the adduct thereby creating an emulsion which is quickly quenched causing the solidification of the adduct in form of spherical particles.
  • spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648 .
  • the so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is of lower than 3, preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl4; the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiCl4 can be carried out one or more times.
  • the electron donor compound can be added in the desired ratios during the treatment with TiCl4.
  • the alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3, possibly in mixture with the above cited trialkylaluminums.
  • the Al/Ti ratio is higher than 1 and may preferably range between 50 and 2000.
  • silicon compounds (iii) in which a is 1, b is 1, c is 2, at least one of R7 and R8 is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionally containing heteroatoms and R9 is a C1-C10 alkyl group, in particular methyl.
  • Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane.
  • C donor methylcyclohexyldimethoxysilane
  • D donor dicyclopentyldimethoxysilane
  • diisopropyldimethoxysilane (2-ethylpipe
  • examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.
  • the external electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said external electron donor compound (iii) of from 0.1 to 200, preferably from 1 to 100 and more preferably from 3 to 50.
  • the polymerization process can be carried out in gas-phase, operating in one or more fluidized or mechanically agitated bed reactors, slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium.
  • liquid monomer for example propylene
  • the heterophasic composition used in the present disclosure is obtained with a sequential polymerization process in two or more stages in which component (a) is obtained in the first stage and then component (b) is obtained in the second stage in the presence of component (a).
  • Each stage can be in gas-phase, operating in one or more fluidized or mechanically agitated bed reactors, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium.
  • liquid monomer for example propylene
  • hybrid processes in which one stage, preferably that in which component (a) is prepared, is carried out in liquid monomer and another stage, preferably that in which the component (b) is prepared, is carried out in gas-phase.
  • component (a) is prepared in a gas-phase reactor, as described EP 782587 , comprising a first and in a second interconnected polymerization zone to which propylene and optionally ethylene are fed in the presence of a catalyst system and from which the polymer produced is discharged.
  • the growing polymer particles flow through the first of said polymerization zones (riser) under fast fluidization conditions, leave said first polymerization zone and enter the second of said polymerization zones (downcomer) through which they flow in a densified form under the action of gravity, leave said second polymerization zone and are reintroduced into said first polymerization zone, thus establishing a circulation of polymer between the two polymerization zones.
  • the conditions of fast fluidization in the first polymerization zone is established by feeding the monomers gas mixture below the point of reintroduction of the growing polymer into said first polymerization zone.
  • the velocity of the transport gas into the first polymerization zone is higher than the transport velocity under the operating conditions and is normally between 2 and 15 m/s.
  • the second polymerization zone where the polymer flows in densified form under the action of gravity, high values of density of the solid are reached which approach the bulk density of the polymer; a positive gain in pressure can thus be obtained along the direction of flow, so that it becomes possible to reintroduce the polymer into the first reaction zone without the help of mechanical means.
  • a "loop" circulation is set up, which is defined by the balance of pressures between the two polymerization zones and by the head loss introduced into the system.
  • one or more inert gases such as nitrogen or an aliphatic hydrocarbon, are maintained in the polymerization zones, in such quantities that the sum of the partial pressures of the inert gases is preferably between 5 and 80% of the total pressure of the gases.
  • the various catalyst components are fed to the first polymerization zone, at any point of said first polymerization zone. However, they can also be fed at any point of the second polymerization zone.
  • Molecular weight regulators known in the art, particularly hydrogen can be used to regulate the molecular weight of the growing polymer. Should a bimodal set-up be desired the use of a barrier stream as described EP-A-1012195 separating the polymerization environment of riser and downer can be used.
  • the polymerization is may be carried out at temperature of from 20 to 120°C, preferably of from 40 to 80°C.
  • the operating pressure may range between 0.5 and 5 MPa, preferably between 1 and 4 MPa.
  • the operating pressure may range between 1 and 8 MPa, preferably between 1.5 and 5 MPa.
  • Hydrogen can be used as a molecular weight regulator.
  • the final heterophasic composition comprising (a)+(b) can be subject to a chemical treatment with organic peroxides in order to lower the average molecular weight and increase the melt flow index up to the value needed for the specific application.
  • the final composition comprising the components (a)-(c) may be added with conventional additives, fillers and pigments, commonly used in olefin polymers such as nucleating agents, extension oils, mineral fillers, and other organic and inorganic pigments.
  • fillers and pigments commonly used in olefin polymers
  • nucleating agents such as nucleating agents, extension oils, mineral fillers, and other organic and inorganic pigments.
  • inorganic fillers such as talc, calcium carbonate and mineral fillers
  • Talc can also have a nucleating effect.
  • the nucleating agents are added to the compositions of the present disclosure in quantities ranging from 0.05 to 2% by weight, more preferably from 0.1 to 1% by weight, with respect to the total weight, for example.
  • the polypropylene composition object of the present disclosure can be used for obtaining injection moulded articles for a variety of objects. Particularly preferred is the use of the polypropylene compositions for the preparation automotive battery cases.
  • composition employing r-PE does not show any worsening of the properties with respect to compositions employing virgin PE with similar features.
  • the content of the xylene-soluble fraction is expressed as a percentage of the original 2.5 grams and then, by the difference (complementary to 100%), the xylene insoluble percentage (%);
  • the sample is dissolved in tetrahydronaphthalene at 135 °C and then poured into a capillary viscometer.
  • the viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows for temperature control with a circulating thermostatic liquid.
  • the downward passage of the meniscus is timed by a photoelectric device.
  • the peak of the S ⁇ carbon (nomenclature according to " Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode " C. J. Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977, 10, 536 ) was used as internal reference at 29.9 ppm.
  • the samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120°C with a 8 % wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove 1H-13C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.
  • the tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmT ⁇ (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm).
  • the melting point has been measured by using a DSC instrument according to ISO 11357-3, at scanning rate of 20°C/min both in cooling and heating, on a sample of weight between 5 and 7 mg., under inert N 2 flow. Instrument calibration made with Indium.
  • the peak of the CH 2 ethylene was used as internal reference at 29.9 ppm.
  • the samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120°C with a 8 % wt/v concentration.
  • Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove 1 H- 13 C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.
  • the polymerization was carried out in the presence of a catalyst system in a series of two reactors equipped with devices to transfer the product from one reactor to the one immediately next to it.
  • the solid catalyst component described above was contacted at 12° C for 24 minutes with aluminium triethyl (TEAL) and dicyclopentyldimethoxysilane (DCPMS) as outside-electron-donor component.
  • TEAL aluminium triethyl
  • DCPMS dicyclopentyldimethoxysilane
  • the catalyst system is then subjected to prepolymerization by maintaining it in suspension in liquid propylene at 20° C for about 5 minutes before introducing it into the first polymerization reactor.
  • the polymerisation run is conducted in continuous in a series of two reactors equipped with devices to transfer the product from one reactor to the one immediately next to it.
  • the first reactor is a gas-phase polymerization reactor having two interconnected polymerization zones. (riser and downer) as described in the European patent EP 782587 .
  • the second reactor is a fluidized bed gas phase reactors. Polymer (a) is prepared in the first reactor, while polymer (b) is prepared in the second reactor, respectively. Temperature and pressure are maintained constant throughout the course of the reaction. Hydrogen is used as molecular weight regulator.
  • the gas phase (propylene, ethylene and hydrogen) is continuously analysed via gaschromatography.
  • the polymer particles of the heterophasic compositions of example 1 is introduced in a twin screw extruder (Werner-type extruder), wherein they are mixed with 10 wt% (based on the total amount of polyolefins) of QCP5603 ivory (a r-PE commercialized by Lyondellbasell containing 10%wt of PP inclusions) and a standard stabilization package.
  • the polymer particles are extruded under nitrogen atmosphere in a twin screw extruder, at a rotation speed of 250 rpm and a melt temperature of 200-250° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP22195654.3A 2022-09-14 2022-09-14 Compositions de polyoléfines obtenues à partir de polyoléfines recyclées Pending EP4339240A1 (fr)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0045977A2 (fr) 1980-08-13 1982-02-17 Montedison S.p.A. Composants et catalyseurs pour la polymérisation d'oléfines
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
US4522930A (en) 1982-02-12 1985-06-11 Montedison S.P.A. Components and catalysts for the polymerization of olefins
EP0782587A1 (fr) 1995-07-20 1997-07-09 Montell Technology Company bv Procede et appareil de polymerisation en phase gazeuse d'alpha-olefines
EP1012195A1 (fr) 1998-07-08 2000-06-28 Montell Technology Company bv Procede et dispositif de polymerisation en phase gazeuse
WO2000063261A1 (fr) 1999-04-15 2000-10-26 Basell Technology Company B.V. Constituants et catalyseurs de polymerisation d'olefines
WO2001057099A1 (fr) 2000-02-02 2001-08-09 Basell Technology Company B.V. Composants et catalyseurs destines a la polymerisation d'olefines
WO2006067023A1 (fr) * 2004-12-23 2006-06-29 Basell Poliolefine Italia S.R.L. Composition polyolefiniques ayant une bonne resistance au blanchiment
WO2006125720A1 (fr) 2005-05-27 2006-11-30 Basell Poliolefine Italia S.R.L. Compositions polyoléfiniques ayant une bonne résistance au blanchissement
WO2022002601A1 (fr) * 2020-06-30 2022-01-06 Basell Poliolefine Italia S.R.L. Compositions de polyoléfines obtenues à partir de polyoléfines recyclées

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
EP0045977A2 (fr) 1980-08-13 1982-02-17 Montedison S.p.A. Composants et catalyseurs pour la polymérisation d'oléfines
US4522930A (en) 1982-02-12 1985-06-11 Montedison S.P.A. Components and catalysts for the polymerization of olefins
EP0782587A1 (fr) 1995-07-20 1997-07-09 Montell Technology Company bv Procede et appareil de polymerisation en phase gazeuse d'alpha-olefines
EP1012195A1 (fr) 1998-07-08 2000-06-28 Montell Technology Company bv Procede et dispositif de polymerisation en phase gazeuse
WO2000063261A1 (fr) 1999-04-15 2000-10-26 Basell Technology Company B.V. Constituants et catalyseurs de polymerisation d'olefines
WO2001057099A1 (fr) 2000-02-02 2001-08-09 Basell Technology Company B.V. Composants et catalyseurs destines a la polymerisation d'olefines
WO2006067023A1 (fr) * 2004-12-23 2006-06-29 Basell Poliolefine Italia S.R.L. Composition polyolefiniques ayant une bonne resistance au blanchiment
WO2006125720A1 (fr) 2005-05-27 2006-11-30 Basell Poliolefine Italia S.R.L. Compositions polyoléfiniques ayant une bonne résistance au blanchissement
WO2022002601A1 (fr) * 2020-06-30 2022-01-06 Basell Poliolefine Italia S.R.L. Compositions de polyoléfines obtenues à partir de polyoléfines recyclées

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
C. J. CARMANR. A. HARRINGTONC. E. WILKES: "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode", MACROMOLECULES, vol. 10, 1977, pages 536
HUGGINS, M.L., J. AM. CHEM. SOC., vol. 64, 1942, pages 2716

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